Cyanomethyl crotonates



Patented July 10, 1945.

uui rao STATES PATENT orrics CYANOMETHYL cnorouarms David 'r. Mowry, Dayton, 01110, assignor to Moncanto Chemical Company, St. Louis, Mo., a corporation 01' Delaware No Drawing.

4 Claims.

The present :invention relates to new esters of glypolonitrile, more particularly to esters of. 513'- colonitrile with crotonic acid or with betachlorocr'otonic acid, and to methods of producing the same.

The invention has asan object the provision of useful, new-este'rs oi glycolonitrile. Another object of the invention is the preparation of new, unsaturated esters oi ,gll'colonitrile capable of forming copolymersiorfuse in the plastic and coating industries, Still another object is the preparation or new. insecticides and fungicides.

These objects are accomplished by the following invention wherein there are prepared unsaturated esters oigl colonitrile havingthe geheral formula;

CHaCRnCl-LCOQCHzCN wherein Rfstahds for hydrogen or chlorine and t x stands'iorhalogen, i. e., chlorine, bromine,

fluorine or iodine. Insteadoi the sodium cyanide,

P tassium cyanide inay-be used.

Cy" omethyl crotonate or cyanomethyl betachloroc tonat are also obtainableby reaction of a" riitonyl halide or a beta-chlorocrotonyl halide withglycolonitrile in the presence of an organiser] inorganic base, according to the equation:

; omcmcucoocmcir- -Hx Application September Serial No. 504,049

- elasticity.

claimed in copending application Serial No.-

insecticides, the latter compound being especially Valuable for this purpose. The new esters are also of interest as intermediates'in the preparation oi dyestuffs, surface-active agents, for example, synthetic detergents and wetting agents, water-proofing and fire-proofing materials, etc.

Both the crotonate and the chlorocrotonate copolymerize with aliphatic diolefinic'hydrocar bons or their derivatives, for example, butadiene,

isoprene and chloropr'ene, to yield valuable rubbery products of highthermal stability and good Such products are described and 504,045, filed September 27, 1943, in the name of Raymond B. Seymour and David T. Mowry.

While a number of saturated esters of glycolonitrile are known, as far as I have been able to ascertain, unsaturated esters of glycolonitrile have not been previously prepared. Glycolonitrile, itself, polymerizesrather rapidly to a colorless, crystalline mass, and in the prior art its esters were generally prepared by'indirect methods, i. e., giycolonitrile was not employed as a constituent of the reaction mixture in reac-.

tions'involving the preparation of itsesters. For

example, Henry (Bull. 500. chim. (2) 46, 42: Rec.

trav. chim. 24, 170), prepared the acetate, the

propionate and the butyrate of glycolonitrile by reaction of chloroacetonitrile with the .potassium salt of acetic acid, propionic acid or butyric acid, respectively. In the preparation of the benzoate of glycolonltrile, the nitrile was formed in situ, benzoyl chloride being reacted .with a mixture or potassium cyanide and formaldehyde instead.

of with glycolonitrile (J. Aloy and C. Rabaut. Bull -soc. chim. v(4) i3, 457-460). Only in the preparation of the carbonates has glycolonitrile been previously employed as an esterifiable alcowherein stands" for halogen and It stands for hydrogen or chlorine.

Still another method for the-preparation of cyanomethyl crotonate or cyanomethyl betachlorocrotonate involves the dehydrohalogenation oi, cyanpmethyl alpha-chlorobutyrate or cya'honiethyl 'beta-chlorobutyrate, for example, by heating in the presence of quinoline or another basic reacting organic or inorganic comi e wrq esiw e equeflw cmcclacx coonmcn cm.ca:cncoo.cra.cn+nc for hydrogen or chlorine. Cyanomethyl crotonate and cyanomethyl beta-ii chlorocrptonate are of interestas fungicides and hol. -,I n U. 8. Patents Nos. 2,266,199 and 2,307,679,

Hectienbleiknerreacts glycolonitrile with phosgene to obtain glycolonitrile dicarbonate or cyanomethyl chloroformate, respectively. It is well known, however, that phosgene is an especially reactive acyl halide and that its reactivity is not necessarily typical for other acyl halides. Since no acyl halide other than phosgene has been previously reacted with glycolonitrile to yield esters thereof, the production of unsaturated esters of glycolonitrile by reaction of the same with unsaturated acyl halides could not have been anticipated.

Also, although ,a saturated ester of glyc'olo-.

nltrile, i. e., the benzoate, has been previously prepared by reactionof the acyl halide with a mixture oi an alkali metal cyanide and formaldehyde in aqueous solution, the course of a parallel reaction with an unsaturated, instead of a saturated, acyl halide could not have been predicted. Many "unsaturated acyl halides are known ,to undergo auto-condensation or polyutes.

of an aqueous mixture of formaldehyde and an alkali metal cyanide with an unsaturated acyl halide consequently could not, have dicted.

The invention is further illustrated. but not limited, by the following examples:

Example 1 Cuanomethul detonate-To 50 grams (0.52

mol, 45 cc.) of 37.1% formalin and 28 grams (0.55

moi) of. 95% aqueous sodium cyanide in 300 cc. 01 water at a temperature of C. there was added, with vigorous stirring, 52 grams (0.5 mol) of crotonyl chloride during a period of 30 min- The ice-bath, which had been used during the addition of the crotonyl chloride, was then removed and the temperature was allowed to rise to 20 C. while stirring for a period of one hour. At the end of this time the supernatant oil was extracted with ether, washed with an aqueous solution of sodium carbonate and then with dilute hydrochloric acid. Upon evaporation of the ether and distillation of the residue under partial vacuum there was obtained 28 grams of. crude cyanomethyl crotonate, B. P. 103-104 C./ 17 mm.

Following the same procedure, but employing greater amounts of reactants, i. e., 104 grams (1 mol) of crotonyl chloride, grams (1.15 mols) of 95% sodium cyanide 'and 90 cc. (1.04 mols) oi. 37.1% formalin, there was obtained grams theoretical yield) of crude cyanomethyl crotonate, B. P. 103-105 C./17 mm.

Upon'combination of the crude products of the two runs and redistillation there was obtained- 7'7 grams of substantially pure cyanomethyl crotonate, B. P. 6768 C./2 mm., n 1.4482,

analyzing as follows:

Percent Percent Percent:

C H N Calcd. for C H 0,N 57. 60 5.64 11. 20 Found 57. 81 5.92 11.38

Cyanomethyl crotonate is particularly valuableas a copolymerizing agent for butadiene, yielding copolymers having good thermal characteristics and elasticity.

Example 2 Cuanomethyl 'bta-chlomcrotonata-Betachlorocrotonyichloride, B. P. -138 C. was obtained by reaction of phosphorus pentachloride on acetoacetic ester. 51 grams (0.37 mol) of beta-chlorocrotonyl chloride was added dropwise to a mixture consisting of 23 grams (0.4 mol) of been pre:

of substantially pure cyanomethyl beta-chlorocrotonate, B. P. 116 C./18 mm., a 1.4797, and anlyzing as follows:

Percent Percent Percent O H N Calcd. for COHOlNCl Found. 4s. :1

aration of cyanomethyl crotonate or cyanomethyl beta-chlorocrotonate by reaction with a mixture of analkali metal cyanide and formaldehyde, I may also use the corresponding acid anhydrides. However, in this case, the reaction is preferably conducted under anhydrous conditions, employing the acid anhydride in excess in order to act as diluent and using gaseous formaldehyde instead of formalin. In working under anhydrous conditions, hydrogen cyanide may be used instead of the alkali metal cyanide. Hydrogen cyanide may also be substituted for the alkali metal. cyanide, wholly or in part, when reacting the unsaturated acyl halide or acid anhydride with an aqueous mixture of formalin and cyanide.

In preparing cyanomethyl crotonate or cyanomethyi beta-chlo'rocrotonaie by reaction oi. the crotonyl halide or the beta-chiorocrotonyl halide with glycolonitrile, reaction is preferably eflected in an inert solvent, for example, ether, chloroform, carbon tetrachloride, benzene, xylene, etc., and in the presence of a basic material such as quinoline. pyridine, dimethyianiline, morpholines, etc. Such inert solvents and basic materials are also useful in the preparation of the esters by dehydrohalogenation of cyanomethyl butyrate or cyanomethyl beta-chlorobutyrate, although in tions are preferably diluents.

Esteriflcation of glycolonitrile by reaction of the same with crotonic anhydride or beta-chlorocrotonic anhydride also provides a good method for the preparation 01' cyanomethyl crotonate or cyanomethyl beta-chlorocrotonate. While the forms of invention disclosed herein constitute preferred embodiments thereof, it is to be understood that the invention is not limited to these precise forms, and that changes may be made therein without departing from the scope of the invention which is defined in the appended claims.

What I claim is:

1. Compounds of the formula:

CmCR 2 CH.COO.CH:CN

where R is a member of the group consisting of 5 ydrogen and chlorine.

2. Cyanomethyl crotonate.

3. Cyanomethyl beta-chiorocrotonate.

- 4. The process which comprises reacting a compound having the formula:

CHLCR 2 CHCOX where R is a. member of the group consisting of hydrogen and chlorine and X is halogen, with glycolonitrile in an inert solvent.

5 navm 'r. MOWRY.

effected in the absence of these instances the dehydrohalogenating reac-v 

